JP2019031048A - Tubular molded body - Google Patents

Abstract

To provide a cylindrical molded body capable of suppressing penetration of a component having relatively wide range SP values.SOLUTION: There is provided a cylindrical molded body having a cylindrical resin layer I containing a vinylidene chloride copolymer, and a cylindrical resin layer II arranged inside the resin layer I and containing a resin having SP value of 12.0 (cal/cm)or more, and having total thickness of 100 μm or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a tubular molded body.

  Conventionally, containers having various forms have been developed, and foods and drinks, seasonings, cosmetics, medicines, and the like are filled and packaged in the containers and sold. Examples of such containers include containers equipped with spouts such as spouts particularly found in food and beverage packaging, and containers attached to ports and ports connected to ports such as found in clothing packaging. Various proposals have been made. Many of these plugs, ports, and tubes have a cylindrical structure so as to constitute a flow path through which the contents of the container can pass.

  Although the contents to be filled are different, these containers are required to have barrier properties such as oxygen barrier properties and water vapor barrier properties from the viewpoint of suppressing deterioration of the contents (maintenance of quality) and maintaining hygiene. Therefore, each container is often composed of a packaging material having a barrier layer. However, on the other hand, it cannot be said that measures for providing barrier properties are sufficiently implemented for the plugs, ports, and tubes attached to the container. Therefore, even if the container has a barrier property, it is difficult to say that a sufficient barrier property is ensured from the whole container with a stopper.

  In addition, it is difficult to say that a measure for providing a barrier property is sufficiently taken even for a container such as an ink containing tube itself having a cylindrical structure.

  For these problems, several measures have been proposed for suppressing deterioration due to gas permeation and improving the storage stability (see, for example, Patent Documents 1 to 3).

JP 2012-162272 A JP 2006-1623 A JP 2004-66477 A

  By the way, from the viewpoint of suppressing deterioration of the contents in the container, oxygen barrier properties to prevent oxidative deterioration and water vapor barrier properties to prevent drying / moisture deterioration are also necessary, but the flavor and aroma of the contents, etc. A barrier property that prevents volatile components from flowing out of the container is also important. However, the barrier properties specifically problematic in the above prior art are oxygen barrier properties and water vapor barrier properties, and it is difficult to say that sufficient consideration has been given to the barrier properties of the components of the contents.

  This invention is made | formed in view of the said problem, Comprising: It aims at providing the cylindrical molded object which can suppress permeation | transmission of the component which has SP value of a comparatively wide range.

  As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by forming a layer structure of a resin having a predetermined barrier performance and a resin having a predetermined solubility parameter. As a result, the present invention has been completed.

That is, the present invention is as follows.
[1]
A cylindrical resin layer I containing a vinylidene chloride copolymer;
A cylindrical resin layer II that is disposed inside the resin layer I and includes a resin having an SP value of 12.0 (cal / cm ³ ) ^1/2 or more;
The total thickness is 100 μm or more,
A cylindrical molded body.
[2]
The content of vinylidene chloride constituting the vinylidene chloride copolymer is 85% by mass or more,
The vinylidene chloride copolymer has a weight average molecular weight of 5.0 × 10 ⁴ or more.
[1] The cylindrical molded body according to [1].
[3]
The total thickness of the resin layer I and the resin layer II is 30% or more with respect to 100% of the total thickness of the cylindrical molded body.
The cylindrical molded body according to [1] or [2].
[4]
The SP value of the resin constituting the resin layer I is 10 to 11.5 (cal / cm ³ ) ^1/2 .
The cylindrical molded body according to any one of [1] to [3].
[5]
The oxygen permeability of the resin layer I is 10000 mL · μm / m ² · 24 hrs · MPa (23 ° C. · 65% RH) or less,
The cylindrical molded body according to any one of [1] to [4].

  ADVANTAGE OF THE INVENTION According to this invention, the cylindrical molded object which can suppress permeation | transmission of the component which has a comparatively wide range SP value can be provided.

Sectional drawing cut | disconnected in the axial direction of the cylindrical molded object of this embodiment and sectional drawing cut | disconnected in the direction orthogonal to an axial direction are shown. It is sectional drawing showing the barrier plug of this embodiment. It is a side view showing the infusion bag with a tube port provided with the tube port of this embodiment. It is sectional drawing showing the writing instrument provided with the ink storage tube of this embodiment.

  Hereinafter, the embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications are possible without departing from the scope of the present invention. It is.

(Cylindrical compact)
The cylindrical molded body of this embodiment is arranged on a cylindrical resin layer I containing a vinylidene chloride copolymer and on the inner side of the resin layer I, and has an SP value of 12.0 (cal / cm ³ ) ^1/2. A cylindrical resin layer II containing the above resin, and the total thickness is 100 μm or more. The “tubular shaped body” is not particularly limited as long as it is a shaped body having two or more openings formed in a cylindrical shape.

  FIG. 1 shows a cross-sectional view cut in the axial direction and a cross-sectional view cut in a direction orthogonal to the axial direction of the cylindrical molded body of the present embodiment. As shown in FIG. 1, the cylindrical molded body 10 of the present embodiment includes a cylindrical resin layer I and a cylindrical resin layer II disposed inside the resin layer I. By having such a configuration, a mechanism that can suppress the permeation of the substance from the inside to the outside of the cylindrical molded body is considered as follows.

  First, in order for a substance to permeate the resin film, the steps of dissolution of the substance inside the resin film, diffusion according to the concentration gradient of the substance inside the resin film, and detachment of the substance from the opposite surface of the resin film are performed. Need to pass. Here, for example, in the case where the substance hardly dissolves inside the resin film (when the affinity between the resin film and the substance is low), the amount of the substance that reaches the subsequent diffusion and desorption steps decreases. In addition, when the cohesive force (such as intermolecular force of the polymer chain) of the resin constituting the resin film is strong, the substance is difficult to diffuse. Furthermore, when the substance is hardly detached from the resin film (when the affinity between the resin film and the substance is high), the diffusion of the substance in the resin film and the subsequent desorption are difficult to proceed. In addition, even when it is difficult for the substance to dissolve inside the resin film (when the affinity between the resin film and the substance is low), the cohesive force of the resin constituting the resin film (intermolecular force of the polymer chain, etc.) ) Is weak, it can be considered that there are pores through which a substance can pass at the molecular level, and as a result, the barrier property does not increase beyond a certain level. Thus, regarding the material permeability of the resin film, it is necessary to consider various properties in combination. In the present embodiment, the “barrier property” refers to a property that a substance hardly permeates the resin layer.

  In this respect, in the present embodiment, the cylindrical resin layer II containing a resin having a relatively high SP value can be regarded as a layer having a low affinity with a substance having a low SP value, and the inside of the resin film. It can be said that this layer is a layer in which the amount of the substance that hardly dissolves and that leads to subsequent diffusion and desorption steps is small. Further, since the resin layer I disposed outside the resin layer II contains a vinylidene chloride copolymer having a strong cohesive force, even if the substance passes through from the resin layer II side, the substance passes through the resin layer I. Configured to be difficult to diffuse. Therefore, in the present embodiment, it is possible to further improve the barrier property by reducing the amount of the substance that reaches the resin layer I and not allowing permeation of the reached substance. Further, even when a substance having a high SP value reaches the steps of dissolution, diffusion and desorption with respect to the cylindrical resin layer II containing a resin having a relatively high SP value, the affinity with the resin layer I is high. Since it becomes low, it is hard to spread | diffuse and it is possible to improve barrier property.

[Resin layer I]
The resin layer I is a cylindrical layer provided outside the resin layer II in the cylindrical molded body. The resin layer I may contain a vinylidene chloride copolymer as a resin constituting the layer, or may be made of a vinylidene chloride copolymer. From the viewpoint of improving barrier properties, the vinylidene chloride copolymer may be used. It is preferable that it consists of a polymer. A plurality of resin layers I may be formed in the cylindrical molded body.

(Polyvinylidene chloride copolymer)
The monomer that can be copolymerized with the vinylidene chloride monomer in the polyvinylidene chloride copolymer (hereinafter sometimes referred to as “comonomer”) is not particularly limited, and examples thereof include vinyl chloride; methyl acrylate, acrylic Acrylic acid esters such as butyl acid; acrylic acid; methacrylic acid esters such as methyl methacrylate and butyl methacrylate; methacrylic acid; methyl acrylonitrile; vinyl acetate and the like. Among these, vinyl chloride, acrylic acid ester, and methylacrylonitrile are preferable from the viewpoint of a balance between barrier properties and extrusion processability. These copolymerizable monomers may be used alone or in combination of two or more.

  The content of vinylidene chloride constituting the vinylidene chloride copolymer is preferably 85% by mass or more, more preferably 90% by mass or more and less than 100% by mass, and further preferably 95% by mass or more and less than 100% by mass. is there. When the content of vinylidene chloride constituting the vinylidene chloride copolymer is 85% by mass or more, the barrier property is further improved, and the deterioration of contents at room temperature and high temperature tends to be further suppressed.

  The comonomer content of the vinylidene chloride-acrylic acid ester copolymer, vinylidene chloride-methacrylic acid ester copolymer, and vinylidene chloride-methylacrylonitrile copolymer is preferably 1 to 35% by mass, more preferably 1 to 25%. % By mass, more preferably 2 to 15.5% by mass, still more preferably 2 to 10% by mass, still more preferably 4 to 10% by mass, and particularly preferably 5 to 8% by mass. It is. When the comonomer content in the vinylidene chloride copolymer is 1% by mass or more, the melting characteristics during extrusion tend to be further improved. Further, when the comonomer content of the vinylidene chloride copolymer is 35% by mass or less, the barrier property is further improved, and the deterioration of the contents at room temperature and high temperature tends to be further suppressed.

  The comonomer content of the vinylidene chloride-vinyl chloride copolymer is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, still more preferably 1 to 21% by mass, and even more. Preferably it is 3.5-18.5 mass%, More preferably, it is 6-16 mass%, Most preferably, it is 8.5-15.0 mass%. When the comonomer content of the vinylidene chloride copolymer is 1% by mass or more, the melting characteristics at the time of extrusion tend to be further improved. Moreover, when the comonomer content of the vinylidene chloride copolymer is 40% by mass or less, the barrier property is further improved, and the deterioration of contents at room temperature and high temperature tends to be further suppressed.

The weight average molecular weight (Mw) of the polyvinylidene chloride copolymer is preferably 5.0 × 10 ⁴ or more, more preferably 6.0 × 10 ^{4 to} 1.5 × 10 ⁵ , and even more preferably 7 0.0 × 10 ⁴ to 1 × 10 ⁵ . When the weight average molecular weight (Mw) is 5.0 × 10 ⁴ or more, the melting characteristics at the time of extrusion tend to be further improved. In addition, when the weight average molecular weight (Mw) is 1.5 × 10 ⁵ or less, melt extrusion while maintaining thermal stability tends to be possible. In the present embodiment, the weight average molecular weight (Mw) can be determined by a gel permeation chromatography method (GPC method) using a standard polystyrene calibration curve.

(SP value)
The SP value of the resin constituting the resin layer I is preferably 10 to 11.5 (cal / cm ³ ) ^1/2 , more preferably 10.2 to 11.4 (cal / cm ³ ) ^1/2. And more preferably 10.4 to 11.3 (cal / cm ³ ) ^1/2 . When the SP value of the resin constituting the resin layer I is within the above range, the difference in SP value with respect to the resin layer II is increased, and the barrier property tends to be further improved. When the resin constituting the resin layer I includes a vinylidene chloride copolymer, the “SP value of the resin constituting the resin layer I” is the SP value of the entire resin constituting the resin layer I. . When the resin layer I is made of a vinylidene chloride copolymer, the “SP value of the resin constituting the resin layer I” is read as the SP value of the vinylidene chloride copolymer. The SP value can be controlled by selecting the resin and adjusting the comonomer content of the vinylidene chloride copolymer.

In the present embodiment, the “SP value” means a solubility parameter (Solubility Parameter). In the present embodiment, the solubility parameter (SP value) means an amount defined by the following formula when the cohesive energy density is ΔE (cal / mol) and the molecular volume is V (cm ³ / mol). It means a value calculated using the Fedor calculation method shown below.
SP value δ ((cal / cm ³ ) ^1/2 ) = (ΔE / ΔV) ^1/2

  Fedor believes that both the cohesive energy density and molar molecular volume depend on the type and number of substituents. F. Fedors, Polm. Eng. Sci. , 14 [2] 147 (1974). The SP values of substances having similar properties tend to be similar, and the closer the SP value, the more likely they are to be compatible. By calculating and comparing the SP value, it is possible to evaluate mutual solubility. Specific SP values for each resin and how to obtain them can be appropriately determined from those conventionally known.

  The solubility parameter has been studied by various researchers so far, and the calculation method is known in addition to the Fedor calculation method described above, the Hansen calculation method, the Small calculation method, and the like. Among the values calculated by these calculation methods, SP values calculated by different calculation methods cannot be simply compared because the calculation methods are different. For example, when evaluating the mutual solubility of substance A and substance B, It is necessary to compare the SP values of the substances A and B after calculating them by the same Fedor calculation method.

(Oxygen permeability)
The oxygen permeability of the resin layer I at 23 ° C. and 65% RH is preferably 10000 mL · μm / m ² · 24 hrs · MPa or less, more preferably 1000 mL · μm / m ² · 24 hrs · MPa or less, Preferably, it is 100 mL · μm / m ² · 24 hrs · MPa or less. The lower limit of the oxygen permeability of the resin layer I at 23 ° C. and 65% RH is not particularly limited, and is 0 mL · μm / m ² · 24 hrs · MPa (detection limit). In the present specification, “RH” means relative humidity.

When the oxygen permeability of the resin layer I at 23 ° C. and 65% RH is 10000 mL · μm / m ² · 24 hrs · MPa or less, the oxygen barrier property of the cylindrical molded body is further improved and the content is deteriorated. It tends to be more suppressed. Note that the oxygen permeability of the resin layer I at 23 ° C. and 65% RH can be lowered by appropriately selecting and using the resin constituting the resin layer I. The oxygen permeability of the resin layer I at 23 ° C. and 65% RH can be measured by the method described in the examples.

(Water vapor permeability)
The water vapor permeability of the resin layer I at 38 ° C. and 90% RH is preferably 1000 g · μm / m ² · 24 hrs · MPa or less, more preferably 100 g · μm / m ² · 24 hrs · MPa or less, Preferably, it is 10 g · μm / m ² · 24 hrs · MPa or less. The lower limit of the water vapor permeability of the resin layer I at 38 ° C. and 90% RH is not particularly limited, and is 0 g · μm / m ² · 24 hrs · MPa (detection limit).

When the water vapor permeability of the resin layer I at 38 ° C. and 90% RH is 1000 g · μm / m ² · 24 hrs · MPa or less, the water vapor barrier property of the cylindrical molded body is further improved and the content is deteriorated. It tends to be more suppressed. Note that the water vapor permeability of the resin layer I at 38 ° C. and 90% RH can be lowered by appropriately selecting and using the resin constituting the resin layer I. Further, the water vapor permeability of the resin layer I at 38 ° C. and 90% RH can be measured by the method described in Examples.

(Thickness)
The thickness of the resin layer I is preferably 10 to 300 μm, more preferably 20 to 200 μm, and still more preferably 30 to 100 μm. When the thickness of the resin layer I is 300 μm or less, the resin layer I can be configured to be thin. Therefore, the thickness of the cylindrical molded body is reduced, which is advantageous when used for various applications. Specifically, when used as a spout such as a spout, the inner diameter of the extraction channel can be increased without changing the external size of the spout. Further, when used as an ink storage tube, the amount of ink that can be stored tends to increase without changing the external size. Moreover, when the thickness of the resin layer I is 10 μm or more, various barrier properties are further improved, and deterioration of contents at room temperature and high temperature tends to be further suppressed.

[Resin layer II]
The resin layer II is a cylindrical layer provided inside the resin layer I in the cylindrical molded body. Resin layer II are also SP value as the resin constituting the layer is comprise a resin is 12.0 (cal / cm ^{3) 1/2} or more, the SP value is 12.0 (cal / cm ³ ) It may be made of a resin that is ^1/2 or more, but from the viewpoint of improving barrier properties, it should be made of a resin having an SP value of 12.0 (cal / cm ³ ) ^1/2 or more. Is preferred. A plurality of resin layers II may be formed in the cylindrical molded body.

(SP value)
The SP value of the resin constituting the resin layer II is preferably 12.0 (cal / cm ³ ) ^1/2 or more, more preferably 12.0 to 20.0 (cal / cm ³ ) ^1/2 . And more preferably 12.2 to 16.0 (cal / cm ³ ) ^1/2 . When the SP value of the resin constituting the resin layer II is within the above range, the affinity with the nonpolar substance is further lowered, and as a result, the solubility of the nonpolar substance in the resin layer II tends to be further lowered. It is in. The SP value can be controlled by selecting the resin and adjusting the comonomer content of the vinylidene chloride copolymer.

  As the resin satisfying the SP value, known resins can be appropriately used and are not particularly limited. For example, as a resin that satisfies the SP value as a homopolymer, for example, polyamides such as nylon 66 (11.2); polyacrylonitriles such as polyacrylonitrile (14.4); polyethylene terephthalate (12.4), etc. Polyesters of: ethylene vinyl alcohol (14.0); celluloses such as cellulose acetate (12.4) and cellulose (19.8).

(Thickness)
The thickness of the resin layer II is preferably 10 to 300 μm, more preferably 30 to 200 μm, and still more preferably 50 to 150 μm. When the thickness of the resin layer II is 700 μm or less, the resin layer II can be made thin. Therefore, the thickness of the cylindrical molded body is reduced, which is advantageous when used for various applications. Specifically, when used as a spout such as a spout, the inner diameter of the extraction channel can be increased without changing the external size of the spout. Further, when used as an ink storage tube, the amount of ink that can be stored tends to increase without changing the external size. Moreover, when the thickness of the resin layer I is 50 μm or more, various barrier properties are further improved, and deterioration of contents at room temperature and high temperature tends to be further suppressed.

  The total thickness of the resin layer I and the resin layer II is preferably 30% or more, more preferably 40% or more, and further preferably 50% or more with respect to 100% of the total thickness of the cylindrical molded body. is there. When the total thickness of the resin layer I and the resin layer II is 30% or more, various barrier properties tend to be further improved. Further, the upper limit of the total thickness of the resin layer I and the resin layer II is not particularly limited, but is preferably 100% or less with respect to 100% of the total thickness of the cylindrical molded body.

[Resin layer III]
The cylindrical molded body of the present embodiment may further include a resin layer III that does not correspond to the resin layers I and II. Specifically, it may further include a resin layer III containing a vinylidene chloride copolymer and a resin other than a resin having an SP value of 12.0 (cal / cm ³ ) ^1/2 or more. A plurality of resin layers III may be formed in the cylindrical molded body. You may have the resin layer of the resin layer II further.

  Such a resin is not particularly limited, but for example, polyethylene resins such as low density polyethylene, medium density polyethylene, high density polyethylene, and ethylene-α-olefin; polypropylene resins such as homopolypropylene, random polypropylene, and block polypropylene ; Cyclic olefin resin such as cycloolefin polymer; Polycarbonate; Polyester resin such as polyethylene terephthalate and polyethylene terbutyrate; Polystyrene; Acrylic ester resin such as polybutyl acrylate; Methacrylic acid ester such as polymethyl methacrylate and polybutyl methacrylate Resin, acrylic-styrene copolymer, and polymethylpentene resin.

  The thickness of the resin layer III is preferably 10 to 300 μm, more preferably 30 to 200 μm, and still more preferably 50 to 150 μm.

(Other additives)
Each of the above resin layers may contain other additives such as known plasticizers, heat stabilizers, colorants, organic lubricants, inorganic lubricants, surfactants, processing aids, antibacterial agents, and antioxidants as necessary. May be included.

  Although it does not specifically limit as a plasticizer, For example, acetyl tributyl citrate, acetylated monoglyceride, dibutyl sebacate etc. are mentioned.

  The heat stabilizer is not particularly limited, and examples thereof include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, epoxy resins, magnesium oxide, hydrotalcite, and the like.

[Total thickness]
The total thickness of the cylindrical molded body is 100 μm or more, preferably 200 μm or more, more preferably 300 μm or more. When the total thickness of the cylindrical molded body is 100 μm or more, various barrier properties are further improved, and deterioration of contents at room temperature and high temperature tends to be further suppressed. Further, the upper limit of the total thickness of the cylindrical molded body is preferably 1500 μm or less, more preferably 1000 μm or less, and further preferably 750 μm or less. When the total thickness of the cylindrical molded body is 1500 μm or less, the thickness of the cylindrical molded body is reduced, which is advantageous when used for various applications. Specifically, when used as a spout such as a spout, the inner diameter of the extraction channel can be increased without changing the external size of the spout. Further, when used as an ink storage tube, the amount of ink that can be stored tends to increase without changing the external size.

〔Layer structure〕
If the cylindrical molded body of this embodiment is the structure by which the resin layer II was distribute | arranged inside the resin layer I, it will not restrict | limit in particular about another layer structure. For example, the following configurations can be considered. The notation “resin layer II / resin layer I” indicates that the resin layer II and the resin layer I are laminated from the inside to the outside of the cylindrical molded body.
Resin layer II / resin layer I
Resin layer II / resin layer I / resin layer III
Resin layer II / resin layer III / resin layer I
Resin layer II / resin layer III / resin layer I / resin layer III
Resin layer III / resin layer II / resin layer I
Resin layer III / resin layer II / resin layer I / resin layer III
Resin layer III / resin layer II / resin layer III / resin layer I
Resin layer III / resin layer II / resin layer III / resin layer I / resin layer III
Resin layer II / resin layer I / resin layer II / resin layer I

(Oxygen permeability)
The oxygen permeability of the cylindrical molded body at 23 ° C./65% RH is preferably 10000 mL · μm / m ² · 24 hrs · MPa or less, more preferably 1000 mL · μm / m ² · 24 hrs · MPa or less, More preferably, it is 100 mL · μm / m ² · 24 hrs · MPa or less. The lower limit of the oxygen permeability of the cylindrical molded body at 23 ° C. and 65% RH is not particularly limited, and is 0 mL · μm / m ² · 24 hrs · MPa (detection limit). In the present specification, “RH” means relative humidity.

When the oxygen permeability of the cylindrical molded body at 23 ° C. and 65% RH is 10000 mL · μm / m ² · 24 hrs · MPa or less, the oxygen barrier property of the cylindrical molded body is further improved, the content is deteriorated, etc. Tend to be more suppressed. Note that the oxygen permeability of the cylindrical molded body at 23 ° C. and 65% RH can be lowered by appropriately selecting and using the resin constituting the resin layer I and the resin constituting the other layer. Moreover, the oxygen permeability of the cylindrical molded body at 23 ° C. and 65% RH can be measured by the method described in Examples.

(Water vapor permeability)
The water vapor permeability of the cylindrical molded body at 38 ° C. and 90% RH is preferably 1000 g · μm / m ² · 24 hrs · MPa or less, more preferably 100 g · μm / m ² · 24 hrs · MPa or less, More preferably, it is 10 g · μm / m ² · 24 hrs · MPa or less. The lower limit of the water vapor permeability of the cylindrical molded body at 38 ° C. and 90% RH is not particularly limited, and is 0 g · μm / m ² · 24 hrs · MPa (detection limit).

When the water vapor permeability of the cylindrical molded body at 38 ° C. and 90% RH is 1000 g · μm / m ² · 24 hrs · MPa or less, the water vapor barrier property of the cylindrical molded body is further improved, the content is deteriorated, etc. Tend to be more suppressed. The water vapor permeability of the cylindrical molded body at 38 ° C. and 90% RH can be lowered by appropriately selecting and using the resin constituting the resin layer I and the resin constituting the other layer. Moreover, the water vapor permeability of the cylindrical molded body at 38 ° C. and 90% RH can be measured by the method described in the examples.

[Method for producing cylindrical molded body]
The manufacturing method of the cylindrical molded body of the present embodiment includes an extrusion molding step of molding a cylindrical molded body having a resin layer laminated in a cylindrical shape by extrusion molding the resin constituting the resin layers I and II. Have. The extrusion molding method of the cylindrical resin layer is not particularly limited, and a conventionally known method can be used.

[Use]
The cylindrical molded body of the present embodiment includes a barrier plug and a liquid transport tube provided in a container for storing food and the like, a barrier plug and a liquid transport tube provided in a container for storing pharmaceuticals, and other food and pharmaceutical products. It can be suitably used as an ink storage tube such as a barrier plug and a liquid transport tube, a ballpoint pen or a fluorescent pen provided in a container for storing other products. In the present embodiment, the “container” is not particularly limited as long as it is configured to accommodate the contents, and a bag or the like is also included in the concept of the container.

[Barrier plug]
The barrier plug of the present embodiment has a spout body attached to a container, and a cylindrical molded body inserted in the spout main body, and the cylindrical molded body is the cylindrical molded body, The spout body includes a polyolefin resin. FIG. 2 is a sectional view showing the barrier plug. The barrier plug 20 includes a spout main body 22 attached to the container 21 and the cylindrical molded body 10 inserted in the spout main body 22, and the cylindrical molded body externally transfers the contents in the container. The extraction flow path 23 for making it pour into is formed. Such a barrier plug 20 is not particularly limited, but can be manufactured, for example, by injection molding a resin constituting the spout body 22 around the tubular molded body 10.

  Although it does not specifically limit as resin which comprises a spout main body, For example, polyethylene-type resin (henceforth "PE"), such as low density polyethylene, medium density polyethylene, high density polyethylene, and ethylene-alpha olefin; Polypropylene resins such as random, block, etc. copolymers (hereinafter also referred to as “PP”); ethylene-vinyl acetate copolymers (hereinafter abbreviated as EVA); polyamide resins (hereinafter also referred to as “PA”) .); Adhesive resin is mentioned. Among these, polyolefin resin is preferable.

[Container with barrier plug]
The container with a barrier plug according to the present embodiment includes a container and the barrier plug attached to the container. The container has an oxygen permeability of 1000 mL · μm / m ² · 24 hrs · MPa (23 ° C. · 65% RH) or less and a water vapor permeability of 1000 g · µm / m ² · 24 hrs · MPa (38 ° C. · 90 % RH) or less, a laminated film having a resin layer, an laminated film having an aluminum foil layer, and at least one selected from the group consisting of metal-deposited films are preferred.

Although it does not specifically limit as a structural member of a container, For example, oxygen permeability is 1000 mL * micrometer / m < ² > * 24hrs * MPa (23 degreeC * 65% RH) or less, and water vapor permeability is 1000 g * micrometer / m. Examples include at least one selected from the group consisting of a laminate film having a resin layer of ² · 24 hrs · MPa (38 ° C. · 90% RH) or less, a laminate film having an aluminum foil layer, and a metal-deposited film. . Such a container and a container with a barrier plug having a barrier plug attached to the container are also included in the scope of the present embodiment.

  The “container” is not particularly limited, and examples thereof include a container with a stopper, a bag with a stopper, a bottle with a stopper, and the like in which seasonings such as beverages, jelly, and soy sauce are enclosed. Since conventional plugs are inferior in oxygen barrier property and / or water vapor barrier property, even if the container for storing food etc. has oxygen barrier property and water vapor barrier property, it has passed through the plug. There is a problem that oxygen and water vapor deteriorate the contents of the package, or conversely, components in the package contents are diffused to the outside through the plugs. In the food packaging process, from the viewpoint of sterilization and disinfection, the food to be packaged is sealed in a container in a heated state, or the container in which the food is sealed is heated. However, when the plug is exposed to water vapor generated from food during the food packaging process, there is a problem that the barrier properties are further lowered. On the other hand, the barrier plug of this embodiment can suppress deterioration of the food etc. in a package by providing a cylindrical molded object.

[Port for infusion bag]
The port of this embodiment is a port attached to an infusion bag, and includes the cylindrical molded body. As for the type of port, the end of the port is a type of port (hereinafter, referred to as “a closed needle such as an elastic body that is configured so that the hollow needle can be pierced and the liquid does not leak from the pierced gap”. Tube type port (hereinafter referred to as “closed plug type port”), twist-off type connectors that twist and open the top, branch type connectors, connectors with caps, etc. Also called “tube port”). “Tube port” refers to an end (hereinafter also referred to as an “inner end of an infusion bag”) to which an infusion bag is bonded (welded) among the plugs serving as a flow path of the infusion bag, and the outside of the infusion bag. And has an end (hereinafter, also referred to as “connector connection end”) configured to allow connection of various connectors and the like, and is distinguished from a closure plug type port in this respect.

  In FIG. 3, the side view showing the infusion bag with a tube port provided with the tube port is shown. One end (inner end of the infusion bag) of the tubular molded body 10 is connected and welded to the infusion bag 31, and the connector 32 is connected to the other end (connector connection end).

The “infusion bag” is not particularly limited, and examples thereof include packaging in which blood, instillation, water, electrolytes, nutrients and the like are enclosed. Since conventional stoppers and liquid transport tubes are inferior in oxygen barrier properties and / or water vapor barrier properties, even if the container itself containing the medicine has oxygen barrier properties and water vapor barrier properties, There is a problem that oxygen and water vapor permeated therethrough deteriorate the contents of the package, or conversely, components in the contents of the package diverge to the outside through the plugs. Moreover, in the pharmaceutical packaging process, from the viewpoint of sterilization and sterilization, the medicine to be packaged is enclosed in a container in a heated state, or the container in which the medicine is enclosed is heated. However, when the plug is exposed to water vapor generated from a pharmaceutical or the like during the pharmaceutical packaging process, there is a problem that the barrier property is further lowered. On the other hand, the barrier plug of this embodiment can prevent adsorption of nutrients and the like to the container and suppress deterioration of medicines in the package by providing the cylindrical molded body.

[Ink tube]
The ink storage tube of this embodiment is an ink storage tube for storing the ink for writing instruments, and the ink storage tube is the cylindrical molded body. FIG. 4 is a schematic sectional view showing a writing instrument provided with the ink storage tube of the present embodiment. The writing instrument 40 including the ink storage tube 10 of the present embodiment has a pen tip 41 at one end of the ink storage tube 10 and a sealing body 43 for sealing ink in the ink storage portion 42 at the other end. As writing instruments, there are batting type and direct liquid type as classification according to the structure in the container, and there are brush, soft brush, hard brush, etc. as classification according to the type of pen tip, but the ink storage tube of this embodiment is any Can also be used. Although it does not restrict | limit especially as a specific kind, For example, a fountain pen, a ball-point pen, a marker, a sign pen, a felt pen, a brush pen, and these refills are mentioned.

  The ink storage tube can be configured such that ink is guided to the pen tip and can be written by pressurizing the inside of the ink storage portion 42. Since the conventional ink storage tube is inferior in oxygen barrier property and / or water vapor barrier property, there is a problem that the pressure in the space 23 decreases with time. On the other hand, the ink storage tube of the present embodiment includes a cylindrical molded body, thereby suppressing the permeation and deterioration of the ink component in the storage tube and preventing quality deterioration such as ink fading. Become.

[Liquid transport tube]
The liquid transport tube of the present embodiment is made of the cylindrical molded body. The liquid transport tube constitutes a pouring channel for pouring the contents in the container to the outside, and the use thereof is not particularly limited. For example, the liquid transport tube is used for the above-mentioned food or medical infusion bag. What is connected and used is mentioned.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

[Preparation of substitute measurement sample for measuring oxygen permeability and water vapor permeability]
In the measurement of the oxygen permeability and water vapor permeability of the cylindrical molded body and the resin layer I, a substitute measurement which is a multilayer film simulating the layer structure (type of resin, stacking order, thickness ratio of each layer) of the cylindrical molded body A sample and a substitute measurement sample that is a single-layer film of only the resin layer I used for the tubular molded body are respectively produced, and from the measured values of oxygen permeability and water vapor permeability of the substitute measurement sample, cylindrical molding The oxygen permeability and water vapor permeability of the body and the resin layer I were calculated.

The substitute measurement film for the cylindrical molded body has a layer composition ratio similar to that of the cylindrical molded body using a direct inflation apparatus and a co-extrusion multilayer die, and the thickness of the layer is 1 / of that of the cylindrical molded body. It was obtained by forming a multilayer film having a thickness of 10. Moreover, the substitute measuring film of the resin layer I was obtained by forming a film using a direct inflation apparatus so that the thickness of the layer was 25 μm using a single layer die. Hereinafter, the terms “substitute measurement film for cylindrical molded body” and “substitute measurement film for resin layer I” refer to films having the above-described configuration.

By measuring the oxygen permeability and water vapor permeability per thickness of these substitute measurement films, and multiplying the measured values by the thickness of the substitute measurement film, the oxygen permeability and water vapor permeability per 1 μm thickness are obtained. Obtained. Since it can be evaluated that the barrier property is higher as the various transmittances per 1 μm thickness are smaller, the thickness of the cylindrical molded body or the thickness of the resin layer I is obtained by comparing the various transmittances per 1 μm thickness. It is possible to evaluate various barrier properties.
Permeation per 1 μm thickness = Transparency of substitute measurement film × Thickness of substitute measurement film

[Oxygen permeability (OTR)]
The oxygen transmission rate (OTR) was measured according to ASTM D-3985. Specifically, using a Mocon OX-TRAN 2/20, a substitute measurement sample having a predetermined thickness was measured under the conditions of 23 ° C. and 65% RH. The obtained measured value was multiplied by the thickness of the cylindrical molded body or the resin layer I to obtain oxygen permeability per 1 μm thickness (rounded off after the decimal point). The unit of oxygen permeability (mL · μm / m ² · 24 hrs · MPa) indicates the oxygen permeability per 1 μm thickness.

[Water vapor transmission rate (WVTR)]
The water vapor transmission rate (WVTR) was measured according to ASTM F-372. Specifically, a substitute measurement sample having a predetermined thickness was measured under the conditions of 38 ° C. and 90% RH using Mocon PERMATRAN-W398. The obtained measured value was multiplied by the thickness of the cylindrical molded body or the resin layer I to obtain the water vapor permeability per 1 μm thickness (rounded off after the decimal point). The unit of water vapor permeability (g · μm / m ² · 24 hrs · MPa) represents the water vapor permeability per 1 μm thickness.

[Aroma retention evaluation]
In the cylindrical molded bodies obtained in Examples and Comparative Examples, trimethylamine (SP value: 6.9 (cal / cm ³ ) ^1/2 ), limonene (SP value: 8.6 (cal / cm ³ ) ^{1 / 2} ), L-menthol (SP value: 9.6 (cal / cm ³ ) ^1/2 ), methyl salicylate (SP value: 13.7 (cal / cm ³ ) ^1/2 ), 1 g each, Sealed with an aluminum stopper. The tube was placed in a 5 L desiccator and sealed with the side of the tube lying sideways. After the desiccator was stored at 40 ° C. for 1 day, the degree of odor of various reagents leaked into the desiccator from the cylindrical molded body was evaluated according to the following criteria.
◯: No smell at all △: Slight smell is felt ×: It smells clearly

[Example 1]
From the inside, MXD6 polyamide resin (PA; SP value 13.5 (cal / cm ³ ) ^1/2 , manufactured by Mitsubishi Gas Chemical Company, product name S6007), adhesive resin (Glue; manufactured by Mitsui Chemicals, Inc., product name) Admer SE810), vinylidene chloride copolymer (VC11; vinylidene chloride (VDC) / vinyl chloride (VC) = 89/11 (mass%), weight average molecular weight 8 × 10 ⁴ , SP value 11.2 (cal / cm ³⁾ ) ^1/2 , manufactured by Asahi Kasei Co., Ltd.), adhesive resin (Glue), low density polyethylene (PE; manufactured by Asahi Kasei Co., Ltd., product name F1920) It was continuously extruded into a cylindrical shape using the equipped melt extrusion equipment. Thereafter, the outer diameter was adjusted to 10 mm in a cold water tank equipped with an outer diameter sizing device to obtain a cylindrical molded body having a five-layer structure having a thickness of 330 μm. Moreover, the substitute measurement film of the 33-micrometer-thick cylindrical molded object and the substitute measurement film of 25-micrometer-thick resin layer I were obtained using the same resin.

[Example 2]
The same as in Example 1 except that instead of the adhesive resin (Glue) corresponding to the fourth layer counting from the inner layer, it was changed to an ethylene-vinyl acetate copolymer (EVA; product name NUC3765D manufactured by Nihon Unicar Co., Ltd.). Thus, a tubular molded body having a five-layer structure having an outer diameter of 10 mm and a thickness of 330 μm, a substitute measuring film of a tubular molded body having a thickness of 33 μm, and a substitute measuring film of the resin layer I having a thickness of 25 μm were obtained.

Example 3
MXD6 polyamide resin (PA), adhesive resin (Glue), vinylidene chloride copolymer (MA5; vinylidene chloride (VDC) / methyl acrylate (MA) = 95/5 (mass%), weight average molecular weight 8 × 10 from the inside ⁴ , SP value 11.2 (cal / cm ³ ) ^1/2 , manufactured by Asahi Kasei Co., Ltd., adhesive resin (Glue), homopolypropylene (PP; manufactured by Sun Allomer Co., Ltd., product name PL500A) are formed in this order. In this way, continuous extrusion into a cylindrical shape was performed using a melt extrusion equipment equipped with a coextrusion multilayer cylindrical die. Thereafter, the outer diameter was adjusted to 10 mm in a cold water tank equipped with an outer diameter sizing device to obtain a cylindrical molded body having a five-layer structure having a thickness of 330 μm. Moreover, the substitute measurement film of the 33-micrometer-thick cylindrical molded object and the substitute measurement film of 25-micrometer-thick resin layer I were obtained using the same resin.

Example 4
A cylindrical molded body having a five-layer structure with an outer diameter of 10 mm and a thickness of 290 μm, in the same manner as in Example 3, except that the thickness of the adhesive resin (Glue) corresponding to the second and fourth layers in order from the inner layer is changed. And the substitute measuring film of the cylindrical molded object of thickness 29 micrometers and the substitute measuring film of the resin layer I of thickness 25 micrometers were obtained.

Example 5
Except that the thickness in each layer was changed, in the same manner as in Example 3, a cylindrical molded body having a five-layer structure having an outer diameter of 10 mm and a thickness of 100 μm, and a substitute measurement film of a cylindrical molded body having a thickness of 10 μm, a thickness of 25 μm A substitute measurement film for the resin layer I was obtained.

Example 6
Instead of MA5 resin, vinylidene chloride copolymer (MA8; vinylidene chloride (VDC) / methyl acrylate (MA) = 92/8 (mass%), weight average molecular weight 8 × 10 ⁴ , SP value 11.2 (cal / cm ³ ) ^1/2 , manufactured by Asahi Kasei Co., Ltd.) in the same manner as in Example 3, a cylindrical molded body having a five-layer structure with an outer diameter of 10 mm and a thickness of 330 μm, and a cylindrical molding with a thickness of 33 μm A substitute measurement film for body, a substitute measurement film for resin layer I having a thickness of 25 μm, was obtained.

Example 7
Except that the thickness in each layer was changed, in the same manner as in Example 6, a cylindrical molded body having a five-layer structure with an outer diameter of 10 mm and a thickness of 600 μm, and a substitute measurement film of a cylindrical molded body with a thickness of 60 μm, a thickness of 25 μm A substitute measurement film for the resin layer I was obtained.

Example 8
Instead of MA5 resin, vinylidene chloride copolymer (MAN5; vinylidene chloride (VDC) / methylacrylonitrile (MAN) = 95/5 (mass%), weight average molecular weight 8 × 10 ⁴ , SP value 11.3 (cal / cm ³ ) ^1/2 , manufactured by Asahi Kasei Co., Ltd.) in the same manner as in Example 3, a cylindrical molded body having a five-layer structure with an outer diameter of 10 mm and a thickness of 330 μm, and a cylindrical molding with a thickness of 33 μm A substitute measurement film for body, a substitute measurement film for resin layer I having a thickness of 25 μm, was obtained.

Example 9
Implemented except using polyethylene terephthalate (PET; SP value 12.4 (cal / cm ³ ) ^1/2 , Teijin Limited, product name TRN-8580FH) instead of the innermost layer MXD6 polyamide resin (PA) In the same manner as in Example 3, a cylindrical molded body having a five-layer structure having an outer diameter of 10 mm and a thickness of 330 μm, a substitute measuring film of a cylindrical molded body having a thickness of 33 μm, and a substitute measuring film of the resin layer I having a thickness of 25 μm were obtained. .

Example 10
Instead of the innermost MXD6 polyamide resin (PA), an ethylene-vinyl alcohol copolymer (EVOH; SP value 14.0 (cal / cm ³ ) ^1/2 , manufactured by Nippon Synthetic Chemical Co., Ltd., product name Soarnol AT4403B) In the same manner as in Example 3 except that was used, a cylindrical molded body having a five-layer structure having an outer diameter of 10 mm and a thickness of 330 μm, a substitute measuring film for a cylindrical molded body having a thickness of 33 μm, and a resin layer I having a thickness of 25 μm A substitute measurement film was obtained.

[Comparative Example 1]
Low density polyethylene (PE, SP value 8.6 (cal / cm ³ ) ^1/2 ), ethylene-vinyl acetate copolymer (EVA), VC11 resin (manufactured by Asahi Kasei Corporation), ethylene-vinyl acetate copolymer from the inside The layers were continuously extruded into a cylindrical shape using a melt-extrusion equipment equipped with a co-extruded multilayer cylindrical die so that layers were formed in the order of coalescence (EVA) and low-density polyethylene (PE). Thereafter, the outer diameter was adjusted to 10 mm in a cold water tank equipped with an outer diameter sizing device to obtain a cylindrical molded body having a five-layer structure having a thickness of 330 μm. Moreover, the substitute measurement film of the 33-micrometer-thick cylindrical molded object and the substitute measurement film of 25-micrometer-thick resin layer I were obtained using the same resin.

[Comparative Example 2]
Coextrusion from the inside to form layers in the order of polyethylene terephthalate (PET), adhesive resin (Glue), ethylene-vinyl alcohol copolymer (EVOH), adhesive resin (Glue), and homopolypropylene (PP) Using a melt extrusion equipment equipped with a multilayer cylindrical die, continuous extrusion was performed in a cylindrical shape. Thereafter, the outer diameter was adjusted to 10 mm in a cold water tank equipped with an outer diameter sizing device to obtain a cylindrical molded body having a five-layer structure having a thickness of 330 μm. Moreover, the substitute measurement film of the 33-micrometer-thick cylindrical molded object and the substitute measurement film of 25-micrometer-thick resin layer I were obtained using the same resin.

[Comparative Example 3]
Except for changing the thickness of each layer, a cylindrical molded body having a five-layer structure having an outer diameter of 10 mm and a thickness of 50 μm, a substitute measuring film for a cylindrical molded body having a thickness of 5 μm, and a resin having a thickness of 25 μm, as in Example 3. A substitute measurement film for layer I was obtained.

  INDUSTRIAL APPLICABILITY The present invention has industrial applicability as a cylindrical molded body having a high barrier property that can be used for various applications.

Claims (5)

A cylindrical resin layer I containing a vinylidene chloride copolymer;
A cylindrical resin layer II that is disposed inside the resin layer I and includes a resin having an SP value of 12.0 (cal / cm ³ ) ^1/2 or more;
The total thickness is 100 μm or more,
A cylindrical molded body. The content of vinylidene chloride constituting the vinylidene chloride copolymer is 85% by mass or more,
The vinylidene chloride copolymer has a weight average molecular weight of 5.0 × 10 ⁴ or more.
The cylindrical molded body according to claim 1. The total thickness of the resin layer I and the resin layer II is 30% or more with respect to 100% of the total thickness of the cylindrical molded body.
The cylindrical molded body according to claim 1 or 2. The SP value of the resin constituting the resin layer I is 10 to 11.5 (cal / cm ³ ) ^1/2 .
The cylindrical molded object of any one of Claims 1-3. The oxygen permeability of the resin layer I is 10000 mL · μm / m ² · 24 hrs · MPa (23 ° C. · 65% RH) or less,
The cylindrical molded object of any one of Claims 1-4.